Oxygen uptake compositions and preservation of oxygen perishable goods

ABSTRACT

The preservation or extension of the life of oxygen perishable products such as fresh or cooked meats; fresh vegetables and fruits; dried vegetables, fruits and meats; packaged pharmaceuticals or biologicals; open and enclosed marketing display cases of meats, fruits and vegetables; and packaging, warehousing and transportation of meats, fruits, and vegetables is obtained by subjecting such products to an atmosphere obtained from gas permeable packets of an oxygen scavenging composition comprising a sodium carbonate mineral and one or more carboxylic acids. When the environment surrounding the oxygen perishable product is subjected to the packets of gaseous permeable oxygen scavenging compositions, oxygen is taken in by the scavenging composition and also the presence of carbon dioxide in the surrounding environment is enhanced thereby minimizing or eliminating the effect the oxygen on the oxygen perishable products.

RELATED APPLICATIONS

This application claims the benefit of U.S. application Ser. No.14/473,569, filed Aug. 29, 2014, which claims priority to U.S.Provisional Application No. 61/872,783, filed Sep. 2, 2013, which areeach incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to novel oxygen uptake compositionscomprising the mineral trona and a mono-, di- or tri-carboxylic acid,that are useful in the uptake of oxygen from a surrounding atmosphere ofoxygen perishable products by adsorption of oxygen onto the surface ofthe trona/carboxylic acid or scavenging oxygen from the surroundingatmosphere and converting such oxygen into carbon dioxide gas to providean inert environment for oxygen perishable goods. More specifically, thepresent invention relates to the use of the mineral trona, comprisingsodium carbonate and sodium bicarbonate, in combination with a mono-,di- or tri-carboxylic acid for the preservation or pacification ofoxygen perishable goods by the adsorption of oxygen onto thetrona/carboxylic acid surface and/or the conversion of oxygen intocarbon dioxide resulting in the preservation of goods that are subjectto oxygen degradation for prolonged periods of time.

BACKGROUND OF THE INVENTION

Oxygen is essential for sustaining of all aerobic living matter which isinclusive of essentially all known forms of animal and plant life. Inhumans and other forms of animal life, generally the respiratory cyclecomprises breathing in of oxygen which is absorbed in the lungs anddistributed accordingly in the blood, to various organs and iseventually “used” up, i.e. exchanged or converted to carbon dioxide byvarious body interactions and exhaled from the lungs primarily as carbondioxide or other expiratory gases.

On the other hand, plant life is dependent upon carbon dioxide and takesit in where, through photosynthesis, it is metabolized or used by theplant in various processes and is eventually converted and released intothe atmosphere as oxygen.

This life cycle is essential to the living planet and all living speciesis well documented and will not be further addressed in thisspecification.

However, each of these gasses has downsides as well. Oxygen participatesin or causes the degradation of organic materials to which it has beenexposed. This is particularly true with perishable organic materialssuch as fruits, vegetables, grains, meat products, processed foods,powdered products such as flour, pharmaceuticals, and the like which maybe in an atmosphere maintained at ambient temperatures or above. Inother words, the lowering of temperatures and lessening or removal ofavailable oxygen content contributes to lengthening the useful life ofsuch materials. Refrigeration is a common mechanism used to extenduseful life of perishable goods. Unfortunately, refrigeration alsoutilizes substantial amounts of energy to maintain suitably lowtemperatures to achieve desired results.

Oxygen perishable items from the time of gathering or production,whether by reaping, picking, digging, cutting, collecting, butchering,processing, cooking, displaying, packaging or any other means, wheresuch items are present in an open environment for a period of time, aresubject to being exposed to oxygen. Surrounding environments are thosepresent when gathering perishables by any of the above methods as wellas loading, transporting, warehousing, manufacturing or processing,packaging in crates or other shipping containers for overland or seatransport, packaging or sealing in containers for sale, refrigeratedshipping or storage, cooling and sectioning of butchered animals and thelike. An open environment is also inclusive of enclosed or semi-enclosedspaces such as found in display counters holding fruits, meats orvegetable in retail outlets.

Therefore, perishable items may be presented for sale, use ordistribution as counter displays, refrigerated fruit, vegetable andflower stands, refrigerated retail displays for meats and processedfoods, packaged and sealed dry goods such as grains, processed grainssuch as flour, manufactured pharmaceuticals, blood and blood productsand organs for organ transplants, or any other approach when presentedfor harvesting, transportation, processing, packaging, displaying orselling. Similar or equivalent but unmentioned modes of treating anyother oxygen perishable items are to be included.

Subjecting of perishable items to an open atmosphere in the presence ofoxygen and particularly when at ambient or elevated temperatures causesthe perishable items to lose freshness and texture, decay, produceobjectionable odors, and become inedible, unsalable or unusable. Torectify this, means and methods have been sought to lessen theobjectionable results and extend the useful life of perishable items.Most decay or spoilage of perishable items is the result of growth ofaerobic microorganisms or pathogens including bacteria, fungi, viruses,which are of animal or vegetable origin.

U.S. Pat. No. 6,106,775, issued Aug. 22, 2001 discloses devices andmethods for introducing humidity into an atmosphere. The devicecomprises an apertured shell containing an absorbent material insidewhich can absorb and retain water. Evaporation of water is enhanced byplacing a mixture of sodium bicarbonate and acetylsalicylic acid(aspirin) on the absorbent material. The purpose is to humidify producebins, refrigerated produce containers, cheese and meat refrigerators andcontainers of dry food, such as cookies and brown sugar.

Published U.S. Application 20010031298, published Oct. 18, 2001, isindirectly a continuation-in-part of U.S. Pat. No. 6,106,775, andteaches the use of aqueous compositions containing a combination ofsodium bicarbonate and acetylsalicylic acid (aspirin) to maintainrelatively high levels of carbon dioxide in the atmosphere of selectedenvironments to prolong the shelf life of various perishable foods andproducts such as vegetables, fruits, meats, fish, seafood, dairyproducts and dry goods. The aqueous composition can be applied bydirectly bathing or showering a perishable product in the aqueouscomposition or indirectly using absorption devices that carry theaqueous compositions placed in close proximity to a perishable product.

Currently the favored means is by using suitable oxygen absorbers toprevent oxygen from destroying or rendering perishable items unsalableor useless. Most oxygen absorbers presently used are based on ironpowder, iron oxides or iron salts which react with oxygen in thesurrounding atmosphere causing the iron powder or salt to oxidize,further oxidize or rust. When all the iron has oxidized the oxygenabsorbers are loaded and cease to function. The iron containing powderis packaged in plastic bags which are permeable to oxygen. The ironcontaining powder may be formulated with activated charcoal, and saltsto further absorb oxygen or hasten its conversion to an iron oxide.

These oxygen absorbers are not edible and have limited life span whenexposed to the atmosphere. They function best when used in a sealed orclosed environment such as in dry pack canning but are not suitable forfresh produce such as fruits, vegetables, freshly cut and or packagedmeats. In such situations, where oxygen may be present in thesurrounding environment, iron based absorbers have limited utility.Further, iron oxygen absorbers often leave a metallic taste in produce,grains and other products where they have been utilized in a sealedenvironment for an extended period of time.

In view of the foregoing, there is a need for advancements in the artfor compositions and methods providing innovative techniques forpreserving oxygen perishable products. It would be particularly usefulif such preservation compositions and techniques could be used atambient or refrigerated conditions and be endothermic in nature tominimize or preserve ambient temperatures for the extended life ofoxygen perishable products. It would also be advantageous to providepreservation systems and methods that are cost efficient and are safefor use with foods intended for animal and particularly humanconsumption. Any increase in the shelf life of oxygen perishableproducts, such as foods, could have great benefit for many entitiesinvolved in the relevant industries, including growers, transporters,retail outlets such as markets, food outlets, and, ultimately, consumers

SUMMARY OF THE INVENTION

The present invention relates to chemical compositions and associatedapparatus and methods for the uptake of oxygen from oxygen perishableproducts or from within the vicinity of such products and generating andreleasing carbon dioxide into the atmosphere surrounding said products.The oxygen may be either adsorbed on the surface of such compositions orabsorbed by such compositions. In either event oxygen within thevicinity of oxygen perishable products is taken up either by beingabsorbed or adsorbed by a trona/carboxylic acid combination and isconverted into carbon dioxide thereby preserving a life or freshness ofthe oxygen perishable products. Here the term “oxygen uptake” is used inreference to the trona/acid compositions and is inclusive of absorption,adsorption or any other means by which oxygen concentration in theatmosphere surrounding the oxygen perishable goods is lessened oreliminated. Therefore, as used in this disclosure, the terms oxygenuptake and oxygen absorber/oxygen adsorber and the like may be usedinterchangeably.

Trona is a natural mineral composed mainly of sodium carbonate andsodium bicarbonate and is chemically referred to as trisodiumhydrogendicarbonate dehydrate or sodium sesquicarbonate, having theformula: Na₃(CO₃)(HCO₃).2H₂O. Trona is generally mined from salt lakedeposits which can be found in the United States, Africa, China, Turkey,and Mexico. Large stratified deposits are mined in Sweetwater County,Wyo. Other trona deposits are also found in the states of Nevada andCalifornia in the United States. Mined trona can be found in, orprocessed into, various degrees of purification. Some trona may containminute amounts of potassium carbonate and potassium bicarbonate witheven lesser amounts of magnesium and calcium salts and other traceminerals.

Other sodium carbonate minerals, somewhat similar to trona, includegaylussite, natron, prissonite, northupite, nahcolite and thermonatrite.To the extent these sodium carbonate containing minerals arefunctionally used in place of, or as a substitute for trona, they aredeemed to be within the scope of this invention. Therefore, the term“sodium carbonate mineral or minerals” as used herein generically willbe inclusive of trona, gaylussite, natron, prissonite, northupite,nahcolite and thermonatrite, including combinations of these minerals.These sodium carbonate minerals all have an oxygen adsorbing and/orabsorbing capability suitable for use in the present invention.

Trona is a particularly useful sodium carbonate mineral having oxygenadsorbing, or absorbing characteristics and is made up primarily oftrisodium hydrogendicarbonate dihydrate, [Na₃(CO₃)(HCO₃).2H₂O] as theprimary active ingredients. The only intended limitation in definingtrona is that of functionality including oxygen uptake, i.e. adsorptionand/or absorption. To that extent, for purposes of this disclosure,trona and hydrogendicarbonate dihydrate may be used interchangeably.Further, all discussion involving trona is also applicable to othersodium carbonate minerals listed herein and should be considered fullydisclosed as suitable alternatives to trona.

Although not required, the sodium carbonate mineral can be recovered andused directly, e.g. without calcining, recrystallization, purification,etc. In some cases, the sodium carbonate mineral can be separated fromrock or other debris, however can typically be used without substantivemodification of the native mineral other than crushing to a suitablesize.

Trona may sometimes be referred to in older literature as urao ornitrum. Trona is generally processed or purified by calcination toobtain soda ash or sodium carbonate (Na₂CO₃) and is used primarily inglass manufacture. Trona is also used in many other applications rangingfrom animal feed, chemical manufacture, and medicine.

The mono-, di- or tricarboxylic acids that can be utilized may containfrom two to twenty carbon atoms and can be formed of straight, branched,saturated or unsaturated carbon chains and, aromatic moieties and besubstituted or unsubstituted.

The chemical compositions comprise a novel combination of the mineraltrona and one or more mono-, di- or tri-carboxylic acids in appropriateproportions. Trona contains, as primary ingredients, a mixture of sodiumcarbonate and sodium bicarbonate along with minor amounts of otherminerals or mineral salts as noted above. When the combination of tronaand the carboxylic acid are brought together, optionally in the presenceof moisture, an acid/base reaction occurs and carbon dioxide isproduced. Also, testing has shown that when trona and a carboxylic acid,in the presence of moisture, are brought together in an oxygencontaining environment, oxygen is taken up by the reaction and theconcentration of oxygen is diminished or essentially eliminated. This isparticularly relevant when the reaction takes place in the presence ofoxygen perishable goods. It is postulated that the solidtrona/carboxylic acid composition not only reacts in the presence ofmoisture but also serves as an oxygen adsorber or absorber with oxygenbeing adsorbed on the surface of the trona crystals by chemicaladsorption and/or absorbed into the trona/carboxylic acid combinationwhere it chemically interacts with some or all of the components in themixture to cause the oxygen to be converted into carbon dioxide.Presumably the carbonates present in the trona/acid mixture provide thecarbon necessary for the oxygen conversion into carbon dioxide.Laboratory tests, as well as testing in the presence of oxygenperishable goods, shows diminished oxygen content, preservation ofoxygen perishable goods as will be further delineated in thisdisclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

In order that the manner in which the invention, including methods,uses, apparatus, devices or any other means recited, are to be carriedout to obtain the desired advantages and results set forth herein, amore particular description of the invention is illustrated in theattached drawing and the written description which follows. It is to beunderstood that these drawings depict only representative embodiments ofthe invention and are not to be considered as limiting the scope whichis limited only by the attached claims and functional equivalentsthereof.

FIG. 1 is a perspective view of a liquid or gas permeable woven packetof the invention containing a mixture of trona and one or more mon-, di-or tri-carboxylic acids.

FIG. 2 is a partial breakaway view of the packet of FIG. 1 showing thetrona and carboxylic acid particles in the interior of the packet.

FIG. 3 is a perspective view of a gas permeable package of the inventioncontaining a mixture of trona and one or more mono-, di- ortri-carboxylic acids.

FIG. 4 is a partial breakaway view of the packet of FIG. 3 showing thetrona and carboxylic acid particles in the interior of the packet.

FIG. 5 is a perspective view of a gas permeable tube containing, inpartial breakaway, a packet as shown in FIG. 3.

FIG. 6 is a perspective view of a liquid container for holding pieces ofoxygen perishable goods, pieces of ice and packets of gas and liquidpermeable packets as shown in FIG. 1.

FIG. 7 is a perspective view of a container or crate holding oxygenperishable goods for shipment and also containing one or more packets asshown in FIG. 3.

FIG. 8 is a perspective view of a display stand holding oxygenperishable goods adapted for water spray means and showing packets ofFIG. 3 strategically placed.

FIG. 9 is a perspective view of a refrigerated display case containingoxygen perishable goods and containing a gas permeable tube containingtrona/carboxylic acid packets as shown in FIG. 5.

FIG. 10 is a representation of a storage unit showing shelving, air flowarrows, oxygen absorber packet storage for placing in a warehouse orother storage areas.

FIG. 11 is a partial breakaway view of a cargo shipping container havingplaced therein containers or crates filled with oxygen perishable goodssuch as shown in FIG. 7 for shipment in trucks, railway cars, cargoships, and as air freight.

FIG. 12 is a perspective view of a container having either no lid or aclear lid and holding oxygen perishable goods for display or shipmentand containing gas permeable packets of trona/carboxylic acid toadsorb/absorb oxygen and produce carbon dioxide.

FIG. 13 is a view of a plastic reclosable bag marketing jerky strips andcontaining gas permeable trona/carboxylic acid packet(s).

FIG. 14 is a view of a tray for marketing fresh meat products placed onabsorbent pads for absorbing liquids and also containing gas permeablepackets of trona/carboxylic acid placed on the tray.

FIG. 15 is a view of an absorbent pad for displaying fresh meat productsand absorbing liquids, such a blood, and, in a partial breakaway view,showing granules of trona and mono-, di- or tricarboxylic embedded inthe pad.

FIG. 16 illustrates a sealed No. 10 can for holding grain kernels orother particulate matter and also containing packets of trona/carboxylicacid for absorbing/adsorbing oxygen and forming a carbon dioxideatmosphere within the can.

FIG. 17 illustrates a bottle with a replaceable cap containingpharmaceutical tablets or capsules and also a packet of trona/carboxylicacid to absorb/adsorb oxygen and promote the formation of carbon dioxidewithin the bottle.

FIG. 18 illustrates a beverage stopper having the granular mixturecontained therein for preserving freshness of a beverage.

DETAILED DESCRIPTION OF THE INVENTION

The mineral trona has been described above and such description, to theextent necessary, is incorporated herein.

The carboxylic acids may be any of a wide variety of mono-, di- andtricarboxylic acids. These carboxylic acids may be comprised of mono-,di- or tricarboxylic acids having the general formula:(HOOC)—R—(COOH)_(x-1)where x is an integer of 1, 2 or 3, and R is a saturated or unsaturated,straight, or branched carbon chain having one to eighteen carbon atoms,or an aromatic moiety having six to eighteen carbon atoms which may besubstituted or unsubstituted by OH, COOH, COOM, COOR′, —OR′substituents, where M can be an alkali or alkaline earth metal, andwhere R′ can be saturated or unsaturated, straight, or branched carbonchain having from one to eight carbons, an aromatic moiety having six toeighteen carbon atoms which may be substituted by alkyl groups havingone to eight carbons, OH, COOH, COOM, COOR′, —OR′ substituents, and Mcan be an alkali or alkaline earth metal. For purposes described hereinsalicylic acid and citric acid are particularly useful carboxylic acidswith citric acid providing exceptional results, although othercarboxylic acids can also be used. Suitable carboxylic acids can be usedsingly or in combination with multiple carboxylic acids. Representative,but not inclusive, of such carboxylic acids are found in the followinglistings.Representative of monocarboxylic saturated and unsaturated acids are:

CH₃CO₂H acetic acid CH₃CH₂CO₂H propionic acid CH₃(CH₂)₂CO₂H butyric acidCH(CH₂)₃CO₂H valeric acid CH₃(CH₂)₄CO₂H caproic acid CH(CH₂)₆CO₂Hcaprylic acid CH₃(CH₂)₈CO₂H capric acid CH₃(CH₂)₁₀COOH Lauric acidCH₃(CH₂)₁₂COOH Myristic acid CH₃(CH₂)₁₄COOH Palmitic acid CH₃(CH₂)₁₆COOHStearic Acid CH₃(CH₂)₃CH═CH(CH₂)₇COOH Myristoleic acidCH₃(CH₂)₅CH═CH(CH₂)₇COOH Palmitoleic acid CH₃(CH₂)₈CH═CH(CH₂)₄COOHSapienic acid CH₃(CH₂)₇CH═CH(CH₂)₇COOH Oleic acidCH₃CH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₇COOH α-Linolenic acidRepresentative of monocarboxylic aromatic acids are:

C₆H₄(COOH)₂ [benzene-1,2-dicarboxylic acid] o-phthalic acid o-phthalicacid C₆H₄(COOH)₂ [benzene-1,3-dicarboxylic acid] isophthalic acid orm-phthalic acid C₆H₄(COOH)₂ [benzene-1,4-dicarboxylic acid] terephthalicacid or p-phthalic acid o-HOC₆H₄COOH [o-hydroxybenzoic acid] salicylicacid o-CHOOC₆H₄COOH [o-acetylsalicylic acid] aspirinRepresentative of dicarboxylic saturated and unsaturated acids are:

HOOC—COOH Oxalic acid HOOC—(CH₂)—COOH Malonic acid HOOC—(CH₂)₂—COOHSuccinic acid HOOC—(CH₂)₃—COOH Glutaric acid HOOC—(CH₂)₄—COOH Adipicacid HOOC—(CH₂)₅—COOH Pimelic acid HOOC—(CH₂)₆—COOH Suberic acidHOOC—(CH₂)₇—COOH Azelaic acid HOOC—(CH₂)₈—COOH Sebacic acidHO₂CCH═CHCO₂H Maleic acid (cis form) Fumaric acid (trans form)HO₂CCH═CHCH₂CO₂H Glutaconic acid HO₂C(CH₂)₈CH═CHCO₂H Traumatic acidRepresentative of tricarboxylic acids are:

The ratio of trona to carboxylic acid may vary on a w/w basis. Althoughother ratios may be useful, as a general guideline, the ratio can oftenrange from 200:1 to 5:1, and in some cases can be from 30:0.5 to 5:1.For example, in the case of citric acid, ratios of about 9:1 areparticularly preferred. The ratio can depend on the particularcarboxylic acid, the number of acid groups and other functional groups,the molecular weight and other factors that can be determinedsystematically.

The amount of trona/carboxylic acid will generally be contained in apouch or packet that is permeable to oxygen or oxygen and water or otherliquid depending upon the intended use. Packets can contain measuredweight amounts of this mixture ranging from 0.1 to 50 grams per packetto be used to treat 50 to 500 cubic feet of air surrounding the oxygenperishable goods being treated or protected. When used in a liquidenvironment, such as the cooling of cooked meat segments in a waterreservoir the trona/carboxylic acid packets may also contain from 0.1 to50 grams, in single or multiple packets and used to treat up to 500gallons of water. Preliminary tests have shown two packets containingabout 36 grams each of a 9:1 (w/w) trona/citric acid mixture issufficient to treat 450 gallons of water in order to reduce thetemperature of 900 lbs beef shanks cooked to a temperature of about 150°F. to a marketable temperature in about half the time it took to coolsimilar shanks cooled only by being immersed in water at the sameinitial temperature.

The trona and carboxylic acid can often be provided in a dry particulateform. Although particle size can vary, sizes from about 0.01 mm to about5 mm can be useful, and in many cases ranges from about 0.05 mm to about1.5 mm. Particle size can affect exposed surface area of the dry mixtureand rates of oxygen uptake. Additional materials can optionally be addedto the trona/carboxylic acid mixture such as, but not limited to,stabilizers, colorants, fillers, and the like.

The trona and carboxylic acid compositions can often be enveloped in apacket which holds a predetermined amount of the composition within apacket volume. The packet can be formed to allow oxygen and air topermeate from surrounding environment into the packet volume to contactthe oxygen capturing composition. Packet sides and walls can beperforated or be formed of porous material. Alternatively, a non-porousmaterial can be used which is then opened immediately prior to use. Forexample, packets can be formed of plastic film, perforated plastic film,fabric, paper, or the like. Non-limiting examples of suitable materialsinclude polyester films, polyester terephthalate (PET) films, paper, andthe like. The packets can range in size depending on the application,and often range in dimensions of about 1 cm² to 100 cm².

Packets may be replaced as necessary. Generally, spent or used packetscan be determined by noting a rise in temperature within the monitoredenvironment, oxygen sensors, or other similar approaches. Optionally,one or more packets can be sealed in a transport package which isolatesthe packet(s) from exposure to oxygen until ready for use.

The invention also relates to methods for using packets of the combinedtrona and mono-, di- and tri-carboxylic acids compositions to absorboxygen from and prolong the useable life of a variety of perishableproducts, which may include foods, fresh vegetables and fruits, grainsand other plant products, animal products and the like. Although notrequired, performance of the compositions can often be increased inmoist or humid environments. For instance, a moist or humid atmospherecan be obtained by humidifying or spraying with water vegetables, fruitsor other produce in grocery stores, restaurants, refrigerated trucks, orother locations, where packets containing the trona/acids compositionsare strategically placed thereby maintaining the freshness of theproduce for a period longer than is otherwise possible.

Another method for applying the aqueous composition is to immerse aperishable product within a water bath or other aqueous environment. Forexample, freshly cooked meat under USDA guidelines requires a drop intemperature from cooking temperature, i.e. ˜145° C. to ˜45° in six hoursor less. Upon the trona/carboxylic acid coming into contact with waterand endothermic reaction is produced and the temperature within theimmediate surrounding environment is lowered.

Still another method according to the implementations of the invention,the trona and di- or tri-carboxylic acid combination can be formulatedas a dry mixture and packaged in moisture absorbent devices such asmoisture permeable packets of various sizes that encase the combinedmaterials. These packets can be strategically placed is vicinitiesappropriate to contact with the perishable products when moisture ispresent. For example, the such packets may be constructed and used tointroduce carbon dioxide into and absorb oxygen from produce bins,produce loaded into trucks, railway cars and ships, refrigerators,frozen food lockers, butchered meat storage lockers and directly toproduce to extend the useable life or shelf life of produce beyond whathas been previously possible. The invention can also be used to preventexposed, refrigerated meats, fish, seafood, cheeses, and other similarfoods from prematurely discoloring and spoiling. The shelf life ofcookies, breads, cakes, brown sugar, tortillas, and other dry ornon-refrigerated foods can also be extended according to the presentinvention. When used in transportation or storage in bins, crates, orthe like the transportation means, trucks, train cars, ships etc. willbe refrigerated. The same holds true for display in grocery stores,stands, or other display units where ambient temperatures would hastenproduct degradation. Further, packets of trona and carboxylic acids maybe placed in perforated pipes or other ventilating devices that releasecarbon dioxide and absorb oxygen when activated by moisture. Once it hasbeen determined how many packets of trona and carboxylic acid arerequired for any enclosed environment they can be place in any desiredspace and packet size relative to the material to be treated. It isadvantageous that this material is non-toxic, releases carbon dioxideand, in some manner not fully understood also absorbs oxygen.

While not known for a certainty, as previously noted, it appearsplausible that the atoms of an adsorbed gas, such as oxygen, are indirect chemical combination with the atoms in the surface of the solidtrona carboxylic acid mixture or combinations. These surface oxygenatoms, by reason of their position, may be in a chemical state which issomewhat different from that of the atoms within the body of the solidtrona/carboxylic acid combination. The oxygen atoms adsorbed on thesurface of the trona and/or carboxylic acid mixture may, therefore, beconsidered as chemically combined, and their chemical environment is notessentially different from that of the oxygen atoms just within thebonding “surface” of the trona carboxylic acids combination itself. Itis believed that it is the trona that provides the surface for theoxygen absorption and not the di- or tri-carboxylic acid but ongoingtests are being conducted to verify this belief. What is known is thatit functions in the uptake of oxygen as will be demonstrated below

As in the preceding paragraph, it is not known for a certainty how thesolid trona carboxylic acid mixture or combinations serve as an oxygenabsorber. The interaction of the carbonates or bicarbonates in trona,reacting with the carboxylic acid certainly function, at least in part,as an acid and base releasing carbon dioxide and water. However, thereare additional reactions or interactions that take place when trona, acarboxylic acid and optionally moisture come together that areunexplained in that, oxygen, in addition to that present in thecarbonates, is taken up such that the oxygen in the surroundingatmosphere is reduced or minimized.

The term oxygen uptake composition is used over terms oxygen absorber oroxygen adsorber. Various theories may be postulated but what is knownthrough repeated demonstrations is that the combination of trona andcarboxylic acids within the confines as described herein, and optionallyin the presence of moisture, will reduce, minimize or eliminate thepresence of oxygen in the immediate atmosphere surrounding oxygenperishable goods.

Application of moisture to strategically placed packets of powderedtrona and carboxylic acids can be accomplished by the introduction of anaqueous spray or fogging in of mist into the enclosure containing thepackets and perishable product to be treated. For enclosed structuressuch as display cases, crates, trucks, railway cars, ships, refrigeratedcontainers for meats and other food products, and the like this can bereadily accomplished. One distinct advantage of the trona carboxylicacid mixture is that it produces an endothermic reaction in addition toproviding carbon dioxide and absorbing oxygen and therefore has anadditional cooling effect.

When the combined cooling and oxygen absorption effect of items inbunched or clumped form is required, such as the cooling of large piecesof cooked meat is required, the trona/carboxylic acid composition of theinvention can also be contained in a water and gas permeable packagedform which is added to a water container holding the meat to be cooled.Chunks of ice plus the endothermic action of the trona carboxylic acidpackets in the container accelerates the cooling time. Monitoring thetemperature drop and adding additional packets of trona carboxylic acidpackets and ice makes it possible to reduce the cooling time of suchcooked meat from the required six hours to less than three hours. Asused herein “meat” may be inclusive of flesh from all forms of animallife, preferably used for human consumption. Animal life is broadlydeemed to be inclusive of four-legged animals such as cattle, sheep,swine, deer, elk, moose and the like which are slaughtered and used orpreserved for human consumption. Animals are also inclusive of birds ofall kinds and primarily those used for human consumption and lake,stream or sea life including fish, shell fish and the like.

Oxygen perishable products per se are not limited to any specificcategory of class so long as such product is perishable in the presenceof oxygen and can be passivated or preserved by an oxygen uptakecomposition and in the presence of carbon dioxide, preferably underrefrigerated conditions. Therefore, any product or item such as thosementioned above including products from plants and animals are inclusiveand are exemplified by fruits, vegetables, grains, meats, dairyproducts, processed fruits, and any of the above which have beenprocessed and/or combined into mixtures such as casseroles, soups, bakedgoods, or any other processed form fit within the definition of oxygenperishable goods. In addition to oxygen perishable goods, it may also bepossible to utilize the trona/carboxylic acid compositions to stabilizeor extend shelf life of oxygen scavenging or absorbing chemicals such asfunctioning as an anti-caking agent.

Applying the trona carboxylic acid packets in the environment ofperishable products also has significant advantages over conventionalhumidifying devices. The absorption devices are self-contained unitsthat do not require electrical power or other external energy sources.Accordingly, the packets described herein can be used in manyenvironments where conventional humidifying devices have beenimpractical or impossible. The cost of manufacturing and operating thepackets disclosed herein are less than those associated withconventional humidifying systems, due to the simple design of thepackets, their lack of moving parts, and their ability to operatewithout electricity. Other advantages of using the trona carboxylic acidpackets disclosed herein, include portability, reusability of thepackets in different locations, and ease of use.

FIG. 1 is a perspective view of a liquid or gas permeable woven packet100 having a front 105 a back (not shown) and sealed at the perimeters101, 102, 103 and 104 enveloping a particulate mixture 106 of trona andand one or more mono-, di- or tri-carboxylic acids.

FIG. 2 is a perspective view of the packet 100 as shown in FIG. 2 with acut away—109 in the front 105 exposing the particulate mixture 106consisting of particles of trona 107 and a mono-, di- or tricarboxylicacid 108.

FIG. 3 is a perspective view of a gas permeable only folded plasticpacket 120 having a front 121 a back (not shown) and sealed at theperimeters 123, 124, and 125 enveloping a particulate mixture of tronaand one or more mono-, di- or tri-carboxylic acids (not shown). Optionalperforations 126 can be formed in the plastic film of the packet 120 toallow gases to permeate into and out of the packet. The plastic packetcan be formed of any suitable material such as plastic film, rigidplastic, porous fabric, and the like. Non-limiting examples of suitablepacket material can include polyethylene film, woven or non-wovenfabric, cloth, and the like. The perforations can be patterned alonglines, along a grid, or oriented random positions across one or moresurfaces of the packet.

FIG. 4 is a perspective view of the packet 120 as shown in FIG. 3 with acut away 127 in the front 121 exposing the particulate mixture 106consisting of particles of trona 107 and a mono-, di- or tricarboxylicacid 108. The packet can optionally be folded along fold 122.

FIG. 5 is a perspective view of an elongated gas permeable tube 130having open ends 131 and 132 and containing in partial breakaway 133, atleast one gas permeable packet 120 containing, in granular form, tronaand a mono-, di- or tricarboxylic acid mixture 106 as shown in FIG. 1.Tube 130 can be formed of a material which is aperture such as a metalmesh 134, grid, perforated sheet, or the like.

FIG. 6 is a perspective view of a liquid container 140 filled with water141 holding segments of oxygen perishable goods 142, such as chunks ofcooked meat, in need of rapid cooling, pieces of ice 143 and one or moreliquid and gas permeable packets 100 as shown in FIG. 1 enveloping aparticulate mixture 106 of trona 107 and one or more mono-, di- ortri-carboxylic acids 108.

FIG. 7 is a cut away view of an enclosed shipping crate 145 containingoxygen perishable fruit 146 and having gas permeable packets 120 of thetrona carboxylic acid mixture 106 distributed throughout the crate 145as needed to adsorb/absorb oxygen and produce an atmosphere of carbondioxide surrounding the fruit.

FIG. 8 is a perspective view of a produce display 150 containing oxygendegradable produce such as tomatoes 151, lettuce 152, celery 153 andbroccoli 154 and retained in a moist environment by mean of an aqueousspray 156 fed through a supply line to spray nozzles 156. Also in themoisture containing environment is a gas permeable elongated tube 130,as shown in FIG. 5, containing strategically located gas permeablepackets of granulated trona and a mono-, di- or tri-carboxylic acid (notshown) to absorb/adsorb oxygen form the immediate environment andenhance a presence of carbon dioxide.

FIG. 9 is a perspective view of yet another enclosed refrigerateddisplay container 160 showing oxygen perishable deli vegetables such asolives 161, cauliflower tips 162, carrot sticks 163, and mushrooms 164and having inserted into the interior environment of the container anelongated gas permeable tube 130 as shown in FIG. 5 containing in one ormore gas permeable packets (not shown) containing, in granular form,trona and a mono-, di- or tricarboxylic acid mixture as shown in FIG. 3.

FIG. 10 is a perspective view of a warehouse storage unit 170 containingshelving 171 and ventilated throughout as shown by directional arrows172 and 173. The warehouse is maintained in a moisture or humiditycontrolled environment for the storage of oxygen perishable goods 173.Packets of trona and carboxylic acid as shown in FIG. 3 may bestrategically placed on the shelving 171 to absorb/adsorb oxygen fromenvironment surrounding the perishable goods 173 and replace it with acarbon dioxide environment.

FIG. 11 is a partially cut away view of a shipping container 180 fortransporting prepackaged oxygen perishable goods represented by 181.Goods 181 may be enclosed in containers or crates which may be sealed orin slatted type crates to promote air circulation. The container 180 andprepackaged goods 181 within may be loaded as cargo on a train, truck,ship, airplane or other means of transportation. Packaged within thegoods 181 or in container 180 may be placed any number of trona/acidpackets 120 based on the projected oxygen absorption/adsorption fromwithin the environment of the goods and also bringing about an enhancedpresence of carbon dioxide within the environment of the oxygenperishable goods. The moisture present within the cargo space or holdduring shipping and the determination of how much trona/acid should bepresent and the size of the packets containing the same can bedetermined by one skilled in the art depending on numerous factors,distance of shipping, humidity of the outside environment, volume ofperishable goods being transported, size of the containers, etc.

FIG. 12 is a perspective view of a display or shipping container 185having a transparent or open top 186 and filled with oxygen perishableproduce such as asparagus 187, grapes 188, apples 189 and cucumbers 190,preferably stored in a humidity controlled environment and containinggas permeable packets 120 of trona/carboxylic acid mixtures as shown inFIGS. 3 and 4 wherein the trona/carboxylic acid mixtures are activatedby the presence of moisture within the container and the surroundingenvironment to absorb/adsorb oxygen and enhance the presence of carbondioxide.

FIG. 13 is a front view of a reclosable plastic envelope or bag 200 thatcan be resealed at the top 201 by a zipper type action 202. Insertedinto the bag 200 are strips of jerky 203 or other oxygen perishableproduce having limited moisture content. Also contained within the bagare gas permeable packets 120 of a granular mixture of trona and mono-,di- or tri-carboxylic acids such as shown in FIGS. 3 and 4. Thetrona/carboxylic acid mixture is designed to lessen the oxygen contentand result in an increase in carbon dioxide in the bag interior. Theamount of trona/carboxylic acid is determined so as not to dehydrate thejerky strips such that they become friable. In other words a minimalamount of moisture is to be tolerated in the jerky strips. However, thecarbon dioxide content is sufficient to prevent the strips from beingcontaminated by bacteria, mold, etc. Even with repeated opening andclosing of the bag, the jerky remains free of such contamination.Similar envelopes or bags can be used to store and preserve a widevariety of dehydrated foods such as, but not limited to, fruits,vegetables, nuts, snacks, and the like.

FIG. 14 is a perspective view of a tray 210 or similar type containerhaving placed thereon absorbed pads 211 on which oxygen degradableproduce such as fresh meat 212 can be placed. Exemplary of fresh meat212 is beef, pork, fish and poultry. Illustrated at the meat in FIG. 14is a beef steak. The moisture from the steak will be absorbed by thepads 211. Also on the tray are one or more gas permeable packets 120 ofa granular mixture of trona and mono-, di- or tri-carboxylic acids suchas shown in FIGS. 3 and 4. The tray 210 may be placed in an encloseddisplay case (not shown) where oxygen in the environment surrounding themeat is adsorbed/absorbed by the trona/carboxylic acid mixture in thepackets 120 thereby lessening the oxygen content in this atmosphere andalso resulting in an increase in carbon dioxide in the surroundingenvironment.

FIG. 15 is a top plan view of a gaseous and moisture absorbent pad 220for holding meat or other oxygen perishable produce in an enclosedenvironment (not shown). In partial break away is shown a granularmixture of trona 107 and mono-, di- or tri-carboxylic acids particles108 embedded in this pad 220 for absorbing/adsorbing oxygen from theenvironment surrounding the pad 220 thereby lessening the oxygen contentand also resulting in an increase in carbon dioxide in such environment.

FIG. 16 is a perspective view of a round storage can or container 225,such as a No. 10 can, having a closable top or lid 226 and a sealedbottom 227. The interior 228 of the container may contain oxygendegradable grain kernels 229 such as corn, wheat, barley, rice, and thelike, and also gaseous permeable packets 120 of a granular mixture oftrona and mono-, di- or tri-carboxylic acids. The container 225 may beopened and closed as warranted and some of the grain kernels 229removed. Oxygen in the gaseous space within the container 225 isadsorbed/absorbed by the granular mixture of trona and carboxylic acidwhich prevents spoilage from occurring. Carbon dioxide formed within thecontainer prevents oxidation of the grain kernals and spoilage fromoccurring.

FIG. 17 is a perspective view of a see through storage container 235having a sealed bottom 236 and a closable top 237 for holding dosageunits of medication 238 such as pills, tablets, capsules, lozenges, andthe like. Within the container 235 in addition to the medication 238 isa gas permeable packet or packets 120 of a granular mixture 106 of tronaand mono-, di- or tri-carboxylic acid particles for absorbing/adsorbingoxygen from the environment within the container and surrounding themedication. The container 235 may be opened and closed repeatedly byremoving the top 227 to remove units of medication 238 thereby allowingfor the entrance of oxygen containing outside air. Even with repeatedopening and closing, the oxygen within the interior of the container 235will be absorbed by the trona/carboxylic acid granules for an extendedperiod of time and the carbon dioxide content within the container willbe enhanced preventing the medication from being oxidized and degraded.

In yet another optional application, the granular mixture can be usedwhile microwaving foods. For example, the granular mixture or a packetof the granular mixture can be included within a microwave chamberduring heating of food. The granular mixture is substantially free ofiron or other materials which would cause sparking or bursting. Thus,packets of the granular mixture can be associated with pre-packagedfoods and do not need to be removed by customers upon heating of thefood.

FIG. 18 is a perspective view of a beverage stopper 250 having thegranular mixture 252 oriented within a chamber 254 of the beveragestopper. The beverage stopper can be shaped to fit within an opening ofa wine bottle, carbonated beverage, cooler, beer, or any other beveragecontainer. The stopper can include a top portion 256 which preventsgases from escaping or entering the beverage and a chamber which isfluidly associated with an interior of the beverage container. Optionalflexible spaced flanges 258 can be engageable with inside edges of athroat of the beverage container. The chamber can also include a mesh orperforated edge which retains the granular mixture within the chamberwhile also allowing gases and liquids to pass into the chamber. Presenceof the granular mixture allows for maintaining freshness of the beverageafter opening from a hermetically sealed condition for an extendedperiod of time. Although conditions can vary, freshness of wines, forexample, can be extended from a couple of days to over a week or more.

EXAMPLES Example 1 This Example Demonstrates Oxygen Absorption withTrona/Citric Acid Mixtures

In order to test the oxygen removing capacity of the present invention,an oxygen permeable packet containing trona with citric acid powder, ata weight ratio of 9:1, was placed in a one inch diameter by three inchlong test tube. In an identical tube a one-gram sample of a commercialiron/iron oxide powder, also in an oxygen permeable packet, was testedto compare the oxygen absorbing results of the present invention to aproduct that is presently used commercially. These tubes were sealed for20 minutes after the introduction of the packets. A gaschromatograph-mass spectrometer (GC-MS) was used to analyze the oxygencontent of the air in the tube. Ambient air contains greater than200,000 ppm (parts per million) by weight oxygen. After twenty minutesexposure of the air in the respective tubes, the tube containing thetrona/citric acid sample registered 11.06 ppm of oxygen and tubecontaining the iron/iron oxide sample registered 15.85 ppm oxygen. Thecaps were removed and the tubes were exposed to ambient air for 30minutes with the respective samples remaining in the tubes. The tubeswere then sealed for another 20 minutes and the air in the tubes wasagain analyzed for oxygen using a GC-MS. The trona/citric acid tuberegistered 8.96 ppm oxygen and the iron/iron oxide tube registered 15.23ppm oxygen. Interestingly, the second test showed better oxygen removalresults than the first test particularly for the trona/citric acid.Presumably this is due to the trona/citric acid sample in the tubecontinuing to absorb oxygen even while the tube was open to theatmosphere These tests demonstrate that the trona/citric acid packetabsorbed oxygen significantly better than the iron/iron oxide packet.

Example 2 This Example Confirms the Results of Example 1

It was calculated that 11.6 mg of the trona/citric acid product ofExample 1 would be comparable, on a w/v basis, to a two gram packet ofthe same product in a #10 tin can used for food storage. To furthercompare the oxygen removing capacity of the present invention with thecommercial oxygen absorbing iron/iron oxide product, 11.6 mg of each ofthese products, in a sealed oxygen permeable packet, were placed in aone inch by three inch tube as in Example 1. When the 11.6 mgtrona/citric acid packet was placed in the tube and analyzed after thetube was sealed for 20 minutes as in Example 1, the GC-MS analysisshowed the oxygen content in the tube had been lowered to 43.7 ppm. Whenthe 11.6 mg of iron/iron oxide packet was sealed in the tube for 20minutes, it had reduced the oxygen content to 43.1 ppm. As in Example 1,these tubes were exposed to air for 30 minutes and after the tubes wereagain sealed for 20 minutes, the trona/citric acid tube contained 35.8ppm oxygen and the iron/iron oxide tube contained 40.2 ppm oxygen. Thesetests again demonstrate that the present invention of trona/citric acidremoved oxygen as well as, or better than, the commercially usediron/iron oxide oxygen-absorbing product.

Example 3 This Example Shows Lengthened Shelf Life of Packaged Jerky atAmbient Temperatures

To demonstrate how well the present invention inhibits bacterial growth,an accelerated 12 month test was conducted on a 4 oz. packet of beefjerky. To this sample of beef jerky a one-gram packet of trona/citricacid (9:1 w/w) was added. The beef jerky was contained in a moisture andgas impermeable plastic envelope, and at the conclusion of theaccelerated test, the jerky was removed and analyzed using the AOAC966.23 method and the standard plate count was less than 10 CFU/g. Thecoliform count was determined using the AOAC 991.14 method, and it wasalso found to be less than 10 CFU/g. When the E. Coli count wasdetermined using the same method, it was also found to be less than 10CFU/g. Using AOAC 2003.07 method the Staphylococcus count was also foundto be less than 10 CFU/g. To analyze for Salmonella a modified AOAC998.09 method was used and it was negative in a 25 gram sample. Theyeast and mold were less than 10 CFU/g when the FDA BAM method was used.The moisture content was found to be 15.89 wt. % when it was analyzedusing a Denver IR-200.

Generally, after an accelerated 12 month test, the jerky would be dryand brittle and the bacterial count would be greatly increased. In thistest the moisture content of the jerky packet was essentially the sameas when first packaged. The jerky was not hard but pliable. Furthermore,the bacterial counts were comparable, if not less than, when the jerkywas first packaged. These tests clearly demonstrate that the oxygenremoving capacity of the trona/citric acid prevents the drying out ofand controls the bacterial growth on packaged beef jerky.

Example 4 Jerky

To demonstrate how well the present invention inhibits bacterial growth,an accelerated 12 month test was conducted on a 6 oz. packet of beefjerky in a plastic envelope as in Example 3. The only difference was thesize of the beef jerky (6 oz.) in the packet. To this sample of beefjerky a one-gram gas permeable packet of trona/citric acid (9:1 w/w) wasadded. The beef jerky packet was sealed, and at the conclusion of theaccelerated test, the jerky was analyzed using the AOAC 966.23 methodand the standard plate count was 5500 CFU/g. The coliform count wasdetermined using the AOAC 991.14 method, and it was found to be lessthan 10 CFU/g. When the E. Coli count was determined using the samemethod it was also found to be less than 10 CFU/g. Using AOAC 2003.07method the Staphylococcus count was also found to be less than 10 CFU/g.To analyze for Salmonella a modified AOAC 998.09 method was used and itwas negative in a 25 gram sample. The yeast and mold were less than 10CFU/g when the FDA BAM method was used. The moisture content was foundto be 9.82 wt. % when it was analyzed using a Denver IR-200.

As in Example 3 the moisture content of the jerky packet was essentiallythe same as when first packaged. The jerky was not hard but pliable.Furthermore, the bacterial counts were comparable, if not less than,when the jerky was first packaged. These tests again clearly demonstratethat the oxygen removing capacity of the trona/citric acid prevents thedrying out of and controls the bacterial growth on packaged beef jerky.

Example 5 Jerky

To further confirm the results of Examples 3 and 4 on bacterial growthand moisture content of jerky following an accelerated 12 month test, athird test was conducted on a 4 oz. packet of beef jerky. Thetrona/citric acid content was the same as in Examples 3 and 4. At theconclusion of the tests the bacterial, yeast and mold counts were asreported in Examples 3 and 4. The moisture content of the jerky wasfound to be 16.46 wt. % when it was analyzed using a Denver IR-200. Allof these tests confirm the results of Examples 3 and 4. In other wordsthe oxygen removing capacity of the trona/citric acid prevents thedrying out of and controls the bacterial growth on packaged beef jerky.

Example 6 This Example Shows Rapid Cooling of Cooked Chunks of Meat byMeans of Trona/Citric Acid Mixtures

When large pieces or chunks of meat are cooked, the existing regulationsrequire that such cooked meats are to be cooled from the cookingtemperature, about 150° F., to about 45° F. in not more than six hours.In this example, to four tanks, 4′×4′×4′, was added 450 gallons of waterand 13 blocks of ice (each block weighing about 10 lbs.). To two of thetanks was added two 36 gram packets of trona/citric acid, (9:1 w/w)powder encased in plastic packets permeable to both liquid and gas.Approximately 900 lbs of cooked beef shanks, each shank being about 12to 15 lbs in weight, and which had been cooked at about 150° F. forabout 1.5 hours, was added to each tank. Temperature probes monitoredselected pieces of beef shank at 30 minute intervals at the top, centerand bottom of each tested shank until an average temperature of 80° F.was reached. The shanks in the tubs containing the trona/citric acidpacket reach the 80° F. temperature in an average time of about 1.5hours whereas the tanks not containing the trona/citric acid the packettook about 2 hours. When the meat reached a temperature of about 60° F.the shanks were removed and placed in a cooler room maintained at 30-35°F. The shanks from the trona/citric acid tank reached the desiredtemperature of about 45° F. in the cooler room in about 3 hours whereasthe meat from the untreated tanks took between 5 and 6 hours.

The difference in time between the trona/citric acid cooled shanks andthe plain water cooled shanks results in a significant labor and timesavings and also accelerates the efficiency and throughput of meat fromcooking to final cooling temperature significantly. The financial gainresulting from increased productivity in a shorter period of time is amajor factor in cooked meat production.

Example 7 Perishable Products

In reference to FIGS. 5 and 9, tubes containing packets of trona/acid(9:1 w/w) will enhance the chilling and preservation of perishableproducts within an oxygen containing environment. The oxygen absorbingcapabilities of the trona/acid and the production of carbon dioxide gasstops or slows the growth of spoilage pathogens within such enclosedenvironment. Susceptible spoilage pathogens are inclusive of bacteria,fungi, viruses, and other microorganisms of animal or vegetable origin.Susceptible environments include, but are not limited to, warehouses orsimilar storage facilities to keep perishable products fresh and enhancecooling properties; manufacturing plants to absorb heat from ovens,machinery, outside environment; transportation environments to preserveperishable products for extended periods, i.e. days or weeks; crates orcontainers for shipping overland or overseas to preserve perishableproducts; refrigerated trucks or reefers to enhance energy efficiencyand save on transportation fuel costs while simultaneously chilling andpreserving perishable products; maintaining moisture in meats, andproduce such as fruits and vegetables.

In general the tubes containing trona/acid packets will extend the lifeof perishable products such that they maintain freshness, moisture andreduce or eliminate spoilage depending upon the number of packets andthe amount of trona/acid within the packets.

Example 8 Perishable Goods

Packets as shown in FIGS. 3 and 4 situated in open and closablecontainers containing oxygen perishable goods may be used to extend thelife of such goods even though there are repeated openings and closingsof the containers. This lengthens storage or shelf live even afterrepeated opening/closing of the package or container for days or weeksand also will permit the container to be made of thinner packagingmaterials thus reducing costs.

Example 9 Jerky and Dried Fruit

Into a container as shown in FIG. 13 is placed freshly cured jerkyand/or dried fruit (e.g. pears, apples, peaches, etc.) along with apacket of trona/acid as shown in FIGS. 3 and 4. The oxygen in thecontainer is absorbed by the trona/acid and replaced by carbon dioxideas a result of the interaction of the trona/acid with the oxygen. Thejerky or fruit, when placed in the container, will maintain freshnessfor about 18 months, or even longer if not subjected to the openatmosphere. The amount of trona/acid will depend upon the volume of thefruit to be treated.

Even with continuous opening and closing, the jerky or dried fruit inthe container will remain fresh, i.e. not lose its moisture content, for30 days or longer due to the presence of the trona/acid packets.

Example 10 Produce

The trona/acid packets in the presence of produce, fruits and vegetablesslows the natural decay process which allows such produce to maintainbetter color, texture and smell for up to 30 days from harvest to pointof sale. Even additional days of freshness from the fields to theretailer and in the store may be obtained when produce is properlyhandled and refrigerated. The trona/acid packets removes oxygen andenhances the production of carbon dioxide (CO₂) providing an atmospherehaving bacteriostatic properties that helps to retard the growth ofspoilage bacteria present on fruits and vegetables.

Particularly when the produce is refrigerated, the endothermicproperties of the trona/acid packets will provide an atmosphere whichchills harvested food quickly and naturally and extends the freshness ofthe produce from the fields to the retailer and in the store; extendsrefrigerated shelf life of the produce; reduces the risk of crosscontamination and related liability or the produce; improves the airquality inside refrigerated storage and display cases (See FIG. 9);reduces offensive odors thereby in fewer discards, markdowns andspoilage.

Example 11 Meat

The trona/acid mixture contained in packets is natural, non-toxicproducts. What is beneficial is that this product, when exposed to theoxygen present on the surface of meat or in the atmosphere surroundingthe meat somehow aids in the production of carbon dioxide (CO₂), aninert gas known to have bacteriostatic properties. CO₂ gas is believedto wrap itself around meat creating an envelope that helps retard thegrowth of spoilage bacteria present on meats.

By slowing the natural decay process; meats (including red meat, poultryand fish) maintain better color, texture and smell consistent withfreshness. This property leads to Consumer takeaway, satisfaction andrepeat sales are increased.

Moreover, growers, producers, wholesalers, shippers, manufacturers,processors and retailers will realize immediate benefits when using thecombined trona/acid combinations which will (a) extend the freshnessfrom processing and shipping to the warehouse and in the store; (b)extend refrigerated shelf life of red meat, poultry and fish; (c) reducethe risk of cross contamination and related liability of oxygendegradable products; (d) improve the air quality inside refrigeratedstorage and display cases; (e) reduce offensive odors; and (f) result inthe reduction of discards, markdowns and spoilage of oxygen perishablemeat products.

Example 12 Warehousing and Storage

When used in refrigerated warehouses and storage units, the combinedtrona/carboxylic acid mixture can change the atmospheric conditionswithin the enclosed environment to improve efficiencies in cooling.Temperatures are lowered not only on the oxygen degradable produce andmeats but within the entire warehouse. This cooling results in enhancedpreservation of products along with the ability for products to retaintheir moisture content thereby keeping the produce fresh over a longerperiod of time.

The trona/carboxylic acid mixture is a natural and safe product whichnot only reduces oxygen content within an enclosed atmosphere but alsosomehow, not fully understood, results in the production of carbondioxide (CO₂), which, when removing oxygen from within the immediatevicinity of oxygen perishable products, may serve as an inert gas havingbacteriostatic properties. The carbon dioxide gas settles around theoxygen perishable produce creating an envelope that helps retard thegrowth of spoilage bacteria present on produce such as red meat,poultry, fish, fruits and vegetables.

By slowing the natural oxidation or decay process in produce; fruits andvegetables there will be maintained a better color, texture and smell ofsuch produce. Some of the advantage attributable to the presence oftrona/carboxylic acid packets in sufficient number and strategicallylocated are: (a) extending product freshness in the warehouse; (b)increasing the storage days of products while maintaining fresh meat,fish, produce and dry goods: (c) reducing the risk of crosscontamination and related liability: (d) improving the air flow, airquality and circulation inside refrigerated storage and display cases:(e) reducing offensive odors: (e) minimizing discards, markdowns andspoilage: (f) lowering the temperature of food naturally: (g) chillingharvested food products quickly and naturally: and (h) improving theefficiencies of cooling systems thus reducing power costs.

Example 13 Transportation

Packets containing trona/carboxylic acid mixtures, in appropriateamounts and strategically spaced within a cargo space will protectoxygen perishable goods shipped long distances, i.e. from one country toanother, cross country, and by various means of transportation, such asair cargo, ships, railway, trucks and any other means. If appropriatelyutilized and spaced the trona/carboxylic acid packets will increase thesustainability of such oxygen perishable products and add additionaldays or even weeks of freshness. By placing trona/carboxylic acidpackets in pallets with product or in the shipping area, it will keepthe product cool, maintain moisture in products, minimize or removeoxygen in the environment and surround products with carbon dioxidewhich, in such an environment possesses bacteriostatic properties.

When shipping produce under such conditions the shipper can add extradays of freshness when transporting produce, meats and fish, increasegeographical coverage with additional days while keeping perishablesfresh. By slowing the natural decay process in meats, fish and produceduring shipping and transportation, foods stay fresher longer and arrivein the stores with longer shelf life and less spoilage. As a result themoisture content of the produce will be maintained, the risk of crosscontamination and related liability will be reduced, the air qualityinside the storage area will be improved and offensive odors reduced.The result will be to extend the sustainability and freshness ofperishable products from the fields to the retailer and to the stores,the produce will arrive at the final destination with less spoilage andfewer discards, and there will be an increased area of geographicalcoverage with additional days while keeping perishables fresh.

Example 14 Growers

Growers and producers of fruits and vegetables have found that they maypreserve their products immediately upon being picked and/or harvestedby the use of the trona/carboxylic acid filled packets of thisinvention. As previously stated this trona/acid combination protectsoxygen perishable produce and also results in enhancing an environmentof carbon dioxide (CO₂), which has been shown to have bacteriostaticproperties. Fruits and vegetables are cocooned or enclosed in the stableenvironment protected by the trona/acid combination which allows thissuch produce to retain its moisture content and remain in a picked orharvested state.

By slowing the natural decaying process in produce during harvesting,storage and shipping, which is attributed to the presence of oxygen,foods stay fresh longer and arrive at stores with increased shelf lifeand reduced spoilage.

Example 15 Home Storage/Refrigeration

Within an enclosed atmosphere, such as a refrigerator or pantry, thetrona/carboxylic acid, when appropriately placed in oxygen permeablepackets will extend the freshness of oxygen perishable products for upto about one month. In this regard it will extend the shelf life andretard the growth of bacteria that may be present on meats, jerky, driedfruit, and produce.

By slowing the natural decay process in produce; fruits and vegetablesmaintain better color, texture and smell. Other advantages to be foundare that it will (a) extend the freshness of opened food in enclosedareas up to 30 days; (b) improve the air quality inside homerefrigerators and pantries; (c) be ideal for home food storage and longterm emergency preparedness; (d) reduce the risk of cross contaminationor various produce items; (e) reduce offensive odors; and (f) result inless produce spoilage and fewer discards.

Example 16 Pharmaceuticals

Pharmaceuticals, particularly tablets or capsules, are usually packagedin larger containers for shipment from the manufacturer to a pharmacy orother intermediary. From there the pharmaceuticals may be dispensed asis or divided into smaller containers to pharmacies, hospitals, nursinghomes, extended care facilities. If a prescription item, thepharmaceuticals may be further dispensed in smaller containers. Ifmarketed without a prescription and are placed on a shelf in thepharmacy, supermarket, or other retail outlet for the consumer topurchase they are still considered to be pharmaceuticals for purposes ofthis invention. In each of these events the tablets or capsules aresubjected to an open environment numerous times which may be detrimentalto the viability and stability of the pharmaceutical. This allows thepharmaceutical to be subjected to an oxygen atmosphere. It is notunusual to have a silica gel or similar packet present in the containerto absorb moisture but the oxygen content in the surrounding atmosphereis not reduced.

By placing an appropriate amount of trona/carboxylic acid packets in thecontainer the oxygen present within the container will be absorbed andthe stability of the pharmaceuticals will be enhanced. The containerhaving the trona/carboxylic acid packets will provide an oxygen freeenvironment within its confines and will continue to absorb oxygen andprovide a carbon dioxide (CO₂), environment within the pharmaceuticalcontainer for days and even weeks although the container may berepeatedly opened and closed as the tablets or capsules within aredispensed. Furthermore, the packets additionally reduce moisture contentand can function as a desiccant which can further extend shelf-life ofsensitive pharmaceutical products.

Example 17 Red Blood Cell Transfusions

Although transfusions can be lifesaving, they are not without risk. Incritically ill patients, red blood cell (RBC) transfusions areassociated with increased morbidity and mortality, which may increasewith prolonged RBC storage before transfusion. Red blood cells can bestored from 21 to 42 days if kept refrigerated at 33.8 to 42.8° F. (1 to6° C.) and an approved preservative is added. The mean storage timebefore transfusion in the United States is 17 days. This shelf life canbe extended if packets of these red blood cells are kept in the presenceof trona/acid packets (as shown in FIG. 3). The oxygen absorbingcapabilities and the production of carbon dioxide gas stops or slows thegrowth of pathogens, which help prevent storage lesion—a set ofbiochemical and biomechanical changes which occur during storage withinsuch enclosed environment. Current regulatory measures are in place tominimize red blood cell, RBC, storage lesion—including a maximum shelflife (currently 42 days), a maximum auto-hemolysis threshold (currently1% in the US), together with an average 24-hour post-transfusion RBCsurvival in vivo of more than 75%. These regulatory measures areexceeded when red blood cells are stored in the usual manor in thepresence of trona/acid mixture.

Example 18 Whole Blood Transfusions

Whole blood, unseparated venous blood, can be stored for up to 35 daysif kept refrigerated at 33.8 to 42.8° F. (1 to 6° C.) and an approvedpreservative is added. This shelf life can be extended if packets ofthis whole blood are kept in the presence of trona/acid packets (asshown in FIG. 3). The oxygen absorbing capabilities and the productionof carbon dioxide gas stops or slows the growth of pathogens, which helpprevent storage lesion—a set of biochemical and biomechanical changeswhich occur during storage within such enclosed environment. The storagelesions are reduced by the presence of trona/acid and the transfusionefficacy in a patient is improved. In general the presence of trona/acidpackets will extend the shelf life of whole blood so that it can be usedin blood transfusions, and these blood transfusions will have greaterefficacy.

Example 19 Plasma Transfusions

Plasma and fractionated plasma products benefit by storage in thepresence of trona/acid packets (as shown in FIG. 3). The oxygenabsorbing capabilities and the production of carbon dioxide gas stops orslows the growth of pathogens. These conditions increase the shelf life,and improve the transfusion efficacy in a patient.

Example 20 Organ Transplants

Because most transplanted organs are from deceased donors, the organmust inevitably be stored after its removal from the donor until it canbe transplanted into a suitable recipient. The donor and recipient areoften in different locations, and time is needed to transport the donororgan to the hospital where the recipient is being prepared fortransplantation. Effective, safe, and reliable methods are needed topreserve the organ ex vivo until transplantation can be performed.Acceptable preservation times vary with the organ. Most surgeons preferto transplant the heart within 5 hours of its removal; the kidney cansafely be stored for 40-50 hours, but earlier transplantation ispreferred. Most pancreas transplants are performed after 5-15 hours ofpreservation. Liver transplantations usually are performed within 6-12hours. Hypothermia is the preferred technique of organ preservationbecause it is simple, does not require sophisticated expensiveequipment, and allows ease of transport. Hypothermia is beneficialbecause it slows metabolism. Organs exposed to normothermic ischemiaremain viable for relatively short periods, usually less than 1 hour.However, biodegradable reactions continue; these include theaccumulation of lactic acid, a decrease in intracellular pH,proteolysis, lipolysis, and lipid peroxidation. The oxygen absorbingcapabilities and the production of carbon dioxide gas as disclosedherein stops or slows the growth of pathogens, which help preventstorage lesion—a set of biochemical and biomechanical changes whichoccur during storage within such enclosed environment. In the presenceof trona/acid (FIG. 3) the conditions are improved, and the preservationof organs ex vivo can be extended until transplantation can beperformed.

It should be understood that the foregoing disclosure relates toexemplary embodiments of the invention and that modifications may bemade without departing from the spirit and scope of the invention as setforth in the claims that follow.

The invention claimed is:
 1. A composition for extending the life ofoxygen perishable products comprising a granular mixture of a sodiumcarbonate mineral and citric acid.
 2. The composition according to claim1, wherein the sodium carbonate mineral is a member selected from thegroup consisting of trona, gaylussite, natron, prissonite, northupite,nahcolite, thermonatrite, and combinations thereof.
 3. The compositionaccording to claim 2, wherein the sodium carbonate mineral is trona. 4.The composition according to claim 3, wherein the trona comprises theformula[Na₃(CO₃)(HCO₃).2H₂O].
 5. The composition according to claim 1, whereinthe sodium carbonate mineral is trona and a w/w ratio of trona to citricacid is 200:1 to 5:1.
 6. The composition according to claim 1, whereinthe composition is a granular composition contained in a gas permeablepacket.
 7. The composition according to claim 1, wherein the granularmixture is oriented within a beverage stopper.
 8. The compositionaccording to claim 1, wherein the oxygen perishable goods is a memberselected from the group consisting of fruits, vegetables, flowers, freshand cooked meats, processed foods, whole kernel grains, processedgrains, grain flour, dosage form pharmaceuticals, whole blood, bloodproducts, harvested transplantable organs, and combinations thereof. 9.A composition for extending the life of oxygen perishable productscomprising a granular mixture of a sodium carbonate mineral and an acidwhich is a mono-, di- or tricarboxylic acid, wherein the composition isa granular composition contained in a gas permeable packet.
 10. Thecomposition according to claim 9, wherein the mono-, di- ortricarboxylic acid has the general formula:(HOOC)—R—(COOH)_(x-1) where x is an integer of 1, 2 or 3, and R is asaturated or unsaturated, straight, or branched carbon chain having oneto eighteen carbon atoms, or an aromatic moiety having six to eighteencarbon atoms which may be unsubstituted or substituted by OH, COOH,COOM, COOR′, —OR′ substituents, where M can be an alkali or alkalineearth metal, and where R′ can be saturated or unsaturated, straight, orbranched carbon chain having from one to eight carbons, an aromaticmoiety having six to eighteen carbon atoms which may be substituted byalkyl groups having one to eight carbons, OH, COOH, COOM, COOR′, —OR′substituents, and M can be an alkali or alkaline earth metal.
 11. Thecomposition according to claim 10, wherein, the acid is a memberselected from the group consisting of citric acid and salicylic acid.12. The composition according to claim 10, wherein the acid is citricacid.
 13. The composition according to claim 9, wherein the sodiumcarbonate mineral is a member selected from the group consisting oftrona, gaylussite, natron, prissonite, northupite, nahcolite,thermonatrite, and combinations thereof.
 14. The composition accordingto claim 9, wherein the sodium carbonate mineral is trona.
 15. Thecomposition according to claim 9, wherein the acid is citric acid andthe sodium carbonate mineral is trona and a w/w ratio of trona to citricacid is 200:1 to 5:1.